Modulating the Charge Transfer of D–S–A Molecules: Structures and NLO Properties

Very recently, the investigation of an Li atom doped effect on the “through-space” electronic interaction (S) of a donor–S–acceptor (D–S–A, 1) shows that the Li-doping effect can modulate the first hyperpolarizability of 1 (Dyes Pigm. 2014, 106, 7−13). Can we further enhance the first hyperpolarizability (βtot) of 1 by modulating the charge transfer of D–S–A molecules? The present work indicates that the βtot value can be successfully modulated by replacing the sp2-hybridized CH═CH moiety connected with substituted para-cyclophane (PCP). On the other hand, the NO2 contributes more than NH2 to the βtot value. The results of time-dependent density functional theory (TD-DFT) provide a good explanation for the variation in the βtot value. Interestingly, the βtot value of 3 (4.09 × 103 au) is larger than 1.52 × 103 au of 4, while the difference between the dipole moments (Δμ) of the ground state and the crucial excited state of 3 (2.93 D) is smaller than that of 4 (7.79 D). Further, the charge-transfer excitat...